Polypropylene dyed with metal complexes of azo compounds



United States Patent "ice 3,515,506 POLYPROPYLENE DYED WITH METALCOMPLEXES OF AZO COMPOUNDS James M. Straley and David J. Wallace,Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., acorporation of New Jersey No Drawing. Continuation-impart of applicationSer. No. 394,063, Sept. 2, 1964. This application Feb. 23, 1968, Ser.No. 707,438

Int. Cl. D06p 1/10 U.S. Cl. 8-42 8 Claims ABSTRACT OF THE DISCLOSUREPolypropylene fibers dyed with a complex metal compound containing oneatom of nickel or cobalt in complex union with two moles of certainortho-alkoxyphenylazo-hydroxy-naphthoic acid amides and esters.

This is a continuationin-part of our United States application Ser. No.394,063 filed Sept. 2, 1964 and now abandoned for Metallized AzoCompounds.

This invention relates to polypropylene textile materials, containing anickel or cobalt compound, dyed with certain rnonoazo dyes and, moreparticularly, to polypropylene fibers containing a complex metalcompound of one atom of nickel or cobalt in combination with two molesof certain azo compounds.

The monoazo compounds useful in preparing the dyed polypropylenematerials have the general formula wherein X represents lower alkyl,e.g. methyl, ethyl; Y represents hydrogen; halogen, e.g. chlorine,bromine; lower alkyl; lower alkoxy, e.g. methoxy, ethoxy, butoxy, andlower haloalkyl, e.g. trifluoromethyl, B-chloroethyl and fi-bromobutyl.Z represents lower alkoxy, amino, lower alkylamino, e.g. methylamino,butylamino; morpholino, piperidino, or cyclohexylamino.

Herein lower alkyl group, lower alkoxy group etc., means that from 1 tocarbon atoms are present in the carbon chain of the group.

The azo compounds described above are particularly useful for dyeingpolypropylene textile fibers, yarns and fabrics which contain minoramounts of a salt of nickel or cobalt. The azo compounds do not containin their molecules, groups such as sulfo, carboxyl, alkylsulfonyl orsulfonamido groups since azo compounds containing such groups do notform suitable metal complexes for coloring the polypropylene fibers. Thecompound having the formula l OCH has excellent afiinity for nickelorcobalt-containing polypropylene fibers; however, if the 5-methoxy groupis replaced e.g. by SO H, SO CH or -SO NH the azo compounds do not formsuitable metal complexes for coloring polypropylene.

In general, the dyed polypropylene textile materials possess goodfastness properties, for example to light,

Patented June 2, 1970 washing, gas (atmospheric fumes) and sublimation.However, the non-metallized dyes having the above formula have littleatfinity for non-metallized polypropylene.

Examples of the nickel and cobalt compounds which can be present in thedyed polypropylene materials are nickel chloride, nickel bromide, nickelsulfate, nickel ace tate, nickel cyanide, nickel formate, nickelthiocyanate [Ni(SCN) cobaltous bromide, cobaltous chloride, cobaltousacetate, cobaltous cyanide, cobalt thiocyanato, nickel butyrate, nickelpelargonate, nickel benzoa-te, nickel tartrate, nickel oxalate, nickeladipate, cobalt tartrate, cobalt 2-ethylhexanoate, nickel stearate,nickel phosphate, and the nickel chelate ofbis(p-tetramethylbutylphenol)- sulfide. The amount of the nickel orcobalt compound present in the dyed polypropylene material will varydepending upon the particular compound employed. Generally, good resultsare obtained when the polypropylene materials contain from about 0.02percent to about 1.0 percent, based on the weight of the polypropylene,o nickel or cobalt.

The nickel and cobalt compounds can be incorporated into thepolypropylene by well-known techniques such as blending in a Banburyrnixer or on the rolls of a rubber mill. The nickel and cobalt compoundsshould be finely divided by conventional means such as by ball millingprior to incorporation in the polypropylene.

The polypropylene useful in preparing the dyed fibers of the inventionis a well-known highly crystalline polypropylene which can be melt spunand drafted to provide fibers having good mechanical fibers. Such fibersfind extensive use in the manufacture of carpets. The polypropylenedescribed in Coover and Joyner Canadian Pat. 730,226 granted Mar. 15,1966 is one example of the polypropylene which can be modified with thenickel and cobalt compounds described herein and dyed with the discloseazo compounds. The polypropylene useful in preparing the dyed fibers cancontain, in addition to the metal-azo dye complexes, other additivessuch as stabilizers, pigments, optical brighteners, etc.

When applied to nickel-containing or cobalt-containing polypropylenefibers by conventional techniques, the disclosed azo compounds givedyeings having improved fastness properties, particularly fastness tolight. The light fastness of such dyeings are substantially greater thanthe light fastness of dyeings obtained by using an azo compound in whichthe alkoxy group, in the position ortho to the azo bridge, of thecompounds described herein is replaced with a hydroxy group. Themetal-azo compound complex which the disclosed azo compounds form withnickel or cobalt under ordinary dyeing conditions exhibit superiorstability to light. The complexes of azo compounds having a hydroxygroup on the diazo component ortho to the azo bridge do not form suchstable complexes and therefore exhibit marked fading upon exposureto-light.

Dyed polypropylene fibers having superior color fastness are obtained byapplying to polypropylene, containing a nickel compound, an azo compoundhaving the formula wherein X represents lower alkyl and Z representslower alkylamino.

The azo compounds can be applied to the metal-containing polypropylenefibers according to well-known 3 procedures by dispersing the azocompound in water by means of a dispersing agent. Dyeing of themetal-modified polypropylene fibers can be carried out at the boil.

The following examples further illustrate the preparation of the azocompounds and the application of the compounds to metal-modifiedpolypropylene fibers.

EXAMPLE 1 Preparation of the amides and esters 94 g. of3-hydroxy-2-napthoic acid is slurried in 500 cc. of dry benzenecontaining 3 cc. of dry dimethylformamide. There is added with stirring61.0 g. thionyl chlo ride in about 1 hr. After holding 1 hr. longer atroom temperature, it is heated at 55-60 C. under such vacuum that the SHCl and excess thionyl chloride are removed. Dry air is then sweptthrough the mix to remove the last traces of these materials and the mixfinally brought to room temperature. There is then added dropwise below60 C., 88 g. of n-butylamine. The mix is then held 1.5 hr. at 75 C. andthe benzene distilled off in vacuo. The residue is poured into 2,000 cc.of water containing 200 cc. of alcohol and stirred 30 min. The productis filtered olf, washed with water and airdried. The yield is 6870 g.,M.P. 117-l19 C. Recrystallization from benzene raises the M.P. tol19-120 C. Other amides are made in the same fashion replacing thebutylamine with the desired amine. The unsubstituted3-hydroxy-2-naphthamide is prepared according to Ber. 58, 2845. Thealkyl esters of 3-hydroxy-2-naphthoic acid is prepared by the process ofZ. physik. Chem, 94, 405, or by treating the acid chloride prepared asabove with the appropriate alcohol instead of an amine.

EXAMPLE 2 Preparation of the dye 1.53 g. of 2,5-dimethoxyaniline, 10 cc.of water and 3 cc. cone. HCl are brought to 80 C., filtered, and thefiltrate cooled to 0 C. 0.72 g. of NaNO in 2 cc. of water is added atnear 0 C. and the mix held 1 hr. longer at this temperature. The excessHNO is destroyed by addition of sulfamic acid. The diazo solution thusprepared is added to a stirred solution of 2.43 g. of the product ofExample 1 in 25 cc. of water containing 1.5 g. NaOH and 10 cc. alcoholwith enough crushed ice to bring the temperature to C. The mix isstirred 2 hr. longer without further cooling and diluted to 400 cc. withwater. The dye is filtered otf, Washed with water and air-dried. Theyield is 3.5 g., M.P. 161-4 C. The compound has the formula OCH OHOONHOAH9n EXAMPLE 3 Dyeing polypropylene fabric 50 mg. of the dye ofExample 2 is dissolved in cc. of Z-methoxyethanol and 3 cc. of a 3%sodium-N-methyl- N-oleyl taurate and 3% sodium lignin sulfonate aqueoussolution is added. The bath is made up to a volume of 200 cc. with warmwater and the pH brought to about 4 with acetic acid. 5 g. of a knittedfabric of polypropylene fibers containing about 2% nickel chelate ofbis(p-toctylphenol)sulfide is entered and dyed at the boil for one hour.The dyed fabric is rinsed and scoured for minutes in 300 cc. of watercontaining 2 g. soap and 2 .g. soda ash at 120 F., then dried. Thefabric is dyed a deep bluish-red shade of excellent resistance to theaction of light, laundering and dry-cleaning in perchloroethylene.

4 In the manner of the above examples, azo compounds having the formulaHO CO-Z are prepared and applied to nickel-containing polypropylenefibers to obtain dyeings having excellent fastness properties.

Color of R Z dyed fiber 2-methoxyphenyl -NH isopro 1 Red. Do NH2 py Red.Do -O-ethyl Red.

CHz-C Hz Do Red.

Z-ethoxyphenyl Red. 2,5-dimethoxyphenyl Blue-red.

Do Do. Do D0. D0. Do. Do HOE; Do. 2,5-dibutoxypheny1 NHCH2CH3 Do.zegnneizhoxy-et-butyl- -NHCH2CH2CH;CH3 Red-violet.

p eny Do -0 emyl Do. Do- --NHCN2CH2OCOCH3 D0.2-methoxy-5-methyl-phenyl.. NHzCHzC H(ON) 0 H Red GHQ-0E2 Do- Red.

CH2CH2 Z-methoxy-Schlorophenyl... NHC4H Red. Z-methoxy-itrifluoro- -NH0411 Red.

methylphenyl. 2,5-dimethoxyphenyl NH-cyc1ohexyl Red.

The invention has been described in considerable detail with particularreference to certain preferred embodiments thereof, but it will beunderstood that variations and modifications can be effected within thespirit and scope of the invention as described hereinabove, and asdefined in the appended claims.

We claim:

1. A polypropylene fiber dyed with a complex metal compound containing 1atom of nickel or cobalt in complex union with 2 moles of a monoazocompound having the formula OH CO-Z wherein -X represents lower alkyl;

Y represents hydrogen, halogen, lower alkyl, lower alkoxy, ortrifluoromethyl; and

Z represents lower alkoxy, amino, lower alkylamino,

morpholino, piperidino, or cyclohexyl-arnino.

'2. A dyed polypropylene fiber according to claim 1 wherein Y representslower alkoxy'; and

Z represents lower alkylamino.

3. A dyed polypropylene fiber according to claim 1 wherein the complexmetal compound contains 1 atom of nickel in complex union with 2 molesof a monoazo compound having the formula (I)CH OH CONHCiHt-n 5. A dyedpolypropylene fiber according to claim 1 wherein the complex metalcompound contains 1 atom of nickel in complex union with 2 moles of amonoazo compound having the formula OCH; OH CONHC H 6. A dyedpolypropylene fiber according to claim 1 wherein the complex metalcompound contains 1 atom of nickel in complex union with 2 moles of amonoazo compound having the formula OCH; OH ('JONHC Hn-i 7. A dyedpolypropylene fiber according to claim 1 wherein the complex metalcompound contain-s 1 atom of nickel in complex union with 2 moles of amonoazo compound having the formula 5 OCH; (])H (FONHCgH l l 0 CH 8. Adyed polypropylene fiber according to claim 1 wherein the complex metalcompound contains 1 atom of nickel in complex union with 2 moles of amonoazo compound having the formula OOH OH QONHCHz I OCH ReferencesCited UNITED STATES PATENTS 8/1965 Mory et a1 9699 3/1965 Chapman et al8l55 FOREIGN PATENTS 5/1964 Belgium. 1/ 1961 Great Britain.

DONALD LEVY, Primary Examiner

